Oil-in-water emulsion

ABSTRACT

Disclosed are oil-in-water emulsions containing an aqueous continuous phase, an emulsified oleaginous liquid, and an oligosaccharide mixture composed of sugar units selected from the group consisting of arabinose, mannose, galactose, glucose, xylose, and mixtures thereof, and which consists primarily of pentosans, hexosans, and mixtures thereof, containing from one to ten sugar units. The emulsions preferably also contain an alkaline earth metal oxide or hydroxide, preferably lime. The emulsions may also contain aphrons.

This patent application is a continuation-in-part of patent application Ser. No. 09/121,712 filed Jul. 24, 1998, now U.S. Pat. No. 5,916,849, issued Jun. 29, 1999, and a continuation-in-part of patent application Ser. No. 09/228,515 filed Jan. 11, 1999, now U.S. Pat. No. 5,977,030 to which priority is claimed herein.

BACKGROUND OF THE INVENTION

The invention pertains to aqueous base fluids, in particular, to oil-in-water emulsions which exhibit an enhanced LSRV.

PRIOR ART

It is well known in the oil and gas well drilling and servicing art to employ oil-in-water drilling and servicing fluids. Such fluids have good lubricity and anti-bit balling characteristics. Such emulsions provide increased drilling rate, longer bit life, fewer round trips, less torque on pipe, less drag on pipe, improved hole conditions, light weight muds, and the like.

SUMMARY OF THE INVENTION

I have now determined that oil-in-water emulsions can be prepared using as the emulsifier an oligosaccharide mixture composed of sugar units selected from the group consisting of arabinose, mannose, galactose, glucose, xylose, and mixtures thereof consisting primarily of pentosans, hexosans, and mixtures thereof, containing from one to ten combined sugar units, preferably from one to four combined sugar units, hereinafter referred to as "OSM", and, optionally an alkaline earth metal oxide or hydroxide, preferably lime.

The OSM preferably comprises the water soluble portion of thermally hydrolyzed lignocellulose.

It is an object of the invention to provide oil-in-water emulsions containing an OSM and, preferably, an alkaline earth metal oxide or hydroxide, most preferably lime, as more fully disclosed herein.

It is another object of the invention to enhance the stability of oil-in-water emulsions by incorporating therein an OSM, and optionally, an alkaline earth metal oxide or hydroxide, preferably calcium oxide or hydroxide.

An additional object of the invention is to provide oil-in-water emulsions containing an OSM, and preferably an alkaline earth metal oxide or hydroxide, most preferably lime, which exhibit an elevated LSRV and which contains aphrons as more fully disclosed herein.

While the invention is susceptible of various modifications and alternative forms, specific embodiments thereof will hereinafter be described in detail and shown by way of example. It should be understood, however, that it is not intended to limit the invention to the particular forms disclosed, but, on the contrary, the invention is to cover all modifications and alternatives falling within the spirit and scope of the invention as expressed in the appended claims.

The compositions can comprise, consist essentially of or consist of the stated materials. The method can comprise, consist essentially of, or consist of the stated steps with the stated materials.

PREFERRED EMBODIMENTS OF THE INVENTION

The oligosaccharide mixture (OSM) useful in this invention is composed of sugar units selected from the group consisting of arabinose, mannose, galactose, glucose, xylose, and mixtures thereof consisting of pentosans, hexosans, and mixtures thereof, containing from one to ten combined sugar units, preferably one to four combined sugar units.

The oligosaccharide mixture is preferably obtained from the thermal hydrolysis of lignocellulose materials. The thermal hydrolysis may be carried out in any one of several manners such as by subjecting wood of trees and woody materials of corn stalks, cane, and other vegetable growths to the action of steam under elevated temperatures and pressures. The OSM may also be obtained by acid hydrolysis of lignocelluloses as well as by saccharification of wood. Preferably, however, the thermal hydrolysis is carried out by charging wood chips to a closed chamber (e.g., a gun as set forth in Mason U.S. Pat. No. 1,824,221, incorporated herein by reference), subjecting the chips to pressure of about 200-1200 pounds per square inch and a temperature of about 200-300° C. for approximately 30 minutes to 5 seconds, respectively, in the presence of steam, and then discharging the woody material from the gun through a constricted discharge means therein into a zone of lower pressure, preferably atmospheric pressure, thereby exploding the wood chips into comparatively finely divided elongated fibers. Under this treatment the wood undergoes hydrolysis, and water-insoluble and readily hydrolyzable constituents thereof are rendered soluble or dispersible in water. These water solubles are removed from the fiber, which may be accomplished by washing the fiber in water or by squeezing the fiber with rolls and/or screws and the like apparatus. See for example Boehm U.S. Pat. No. 2,224,135, incorporated herein by reference. The water solubles can be concentrated or rendered solid by removing water therefrom, as by evaporation, drying, etc.

Water solubles resulting from such hydrolysis of lignocellulose materials as a class are applicable to this invention. A typical analysis of the water solubles, the OSM of this invention, made from pine wood is as follows: hexosans and pentosans, 70% by weight; lignin, 15% by weight; non-sugar carbohydrates, 10% by weight; and gums, 5% by weight. The constituents of the OSM will vary somewhat depending on the type of lignocellulose material hydrolyzed and the conditions, e.g., time, temperature, pressure, etc. Depending upon these conditions, the constituents of the OSM can vary roughly as follows: pentosans and hexosans, 60-80% by weight; lignin, 5-25% by weight; non-sugar carbohydrates, 5-15% by weight; and gums, 2-8% by weight. The pentosans and hexosans contain primarily from one to about four combined sugar units composed of arabinose, mannose, galactose, glucose, and xylose sugar units.

Water solubles resulting from the hydrolysis of other polysaccharide-containing materials such as seeds (i.e., cereal grains and other polysaccharide-containing plant products), plant extrudates, waste vegetable materials, and even refined polysaccharide products can also be used as the OSM in this invention.

Oil-in-water emulsions can be prepared by dispersing the OSM in an aqueous liquid and mixing therewith an oleaginous liquid. The higher the shear during mixing, the more stable the emulsion will be, as is well known in the art. The viscosity and stability of the emulsion can be increased by incorporating a viscosifier/suspending agent in the aqueous phase of the emulsion. Other additives to impart specific properties or characteristics to the emulsion can also be added thereto. Preferably there is also added to the oil-in-water emulsion an alkaline earth metal oxide or hydroxide, most preferably calcium oxide or hydroxide.

The oleaginous liquid may be any organic, water insoluble liquid which will form a discrete phase in admixture with the aqueous liquid, such as hydrocarbons, vegetable oils, polypropylene glycols, and the like water insoluble liquids. When the aqueous liquid is a salt solution, organic liquids normally water soluble but which are insoluble in the salt solution may be utilized. Preferred oleaginous liquids are hydrocarbons such as the various fractions refined from petroleum oils, synthetic liquids manufactured from various organic alkenes, acids, ethers, alcohols, and the like, and crude oil, such as polyalphaolefins, internal olefins, carboxylic acid esters, phosphate esters, and the like.

The aqueous liquid may be fresh water, a natural brine, sea water, or a formulated brine. The formulated brine is manufactured by dissolving one or more soluble salts in water, a natural brine, or sea water. Representative salts are the chloride, bromide, acetate, and formate salts of cesium, potassium, sodium, calcium, magnesium, and zinc.

A supplemental emulsifier as is well known in the art can be added to the oil-in-water emulsions of this invention. In this respect, it is another aspect of this invention to add the OSM as disclosed herein, optionally together with an alkaline earth metal oxide or hydroxide (hereinafter sometimes referred to as "AEMOOH") to oil-in-water emulsions to enhance the stability of such emulsions.

The amount of the oleaginous liquid in the emulsion will depend on the concentration of the OSM and the AEMOOH. Increasing the concentration of the OSM increases the viscosity of the emulsion. Increasing the concentration of oil increases the viscosity of the emulsion. The concentration of the AEMOOH is dependent upon the concentration of the OSM. Generally the concentrations of OSM, oleaginous liquid, and AEMOOH will be such as to produce an emulsion having the desired viscosity and stability. In general the emulsion will contain from about 5% to about 75% by volume of the combined liquid phases (oleaginous liquid and aqueous liquid) of the oleaginous liquid, from about 0.5 ppb to about 150 ppb OSM, and from 0 ppb to about 5 ppb AEMOOH. Preferably the emulsion will contain from about 10% to about 50% by volume oil (% v/v), from about 1 ppb to about 20 ppb OSM, and from about 0.5 ppb to about 3 ppb AEMOOH.

The oil-in-water emulsions are useful as well drilling and servicing fluids for various oil and gas well operations, dust control operations, agricultural operations (i.e., as carriers for insecticides, pesticides, and the like), and other uses amenable to oil-in-water emulsions.

If desired, polysaccharides can be incorporated into the oil-in-water emulsions to increase the low shear rate viscosity of the fluid to produce a fluid exhibiting a high yield stress, shear thinning behavior. Particularly useful are biopolymers produced by the action of bacteria, fungi, or other microorganisms on a suitable substrate. Exemplary biopolymers are the polysaccharides produced by the action of Xanthomonas compestris bacteria which are known as xanthan gums. These are available commercially from several sources including: Kelco Oil Field Group, Inc., under the trademarks "Xanvis" and "Kelzan"; Rhone-Poulenc Chimie Fine, under the trademark "Rhodopol 23-p"; Pfizer Inc., under the trademark "Flocon 4800C"; Shell International Chemical Company of London, U.K., under the trademark "Shellflo ZA"; and Drilling Specialties Company, under the trademark "Flowzan." See for example U.S. Pat. No. 4,299,825 and U.S. Pat. No. 4,758,356, each incorporated herein by reference. Other biopolymers useful in the fluids of this invention are the so-called welan gums produced by fermentation with a microorganism of the genus Alcaligenes. See for example U.S. Pat. No. 4,342,866, incorporated herein by reference. Gellan gums are disclosed in U.S. Pat. No. 4,503,084, incorporated herein by reference. Scleroglucan polysaccharides produced by fungi of the genus sclerotium are disclosed in U.S. Pat. No. 3,301,848, incorporated herein by reference. Commercially available scleroglucan is sold under the trademarks "Polytran" from the Pillsbury Company and "Actigum CS-11" from CECA S.A. Succinoglycan polysaccharides are produced by cultivating a slime-forming species of Pesudomonas, Rhizobium, Alcaligenes or Agrobacterium, e.g., Pseudomonas sp. NCIB 11264, Pseudomonas sp. NCIB 11592 or Agrobacterium radiobacter NCIB 11883, or mutants thereof, as described in European Patent No. A40445 or A138255. Commercially available succinoglycan biopolymer is sold by Shell International Chemical Company of London, U.K., under the trademark "Shellflo-S".

Other polysaccharides added to aqueous base borehole fluids to provide characteristics to the fluids other than increasing the low shear rate viscosity include: cellulose derivatives, such as carboxymethyl cellulose, hydroxyethyl cellulose, mixed ethers, and the like, starch derivatives such as carboxymethyl starch, hydroxyethyl starch, hydroxypropyl starch, mixed ethers, and the like, including the partially crosslinked derivatives thereof, guar gum and derivatives thereof, and other polysaccharides as are well known in the art. Such polysaccharides may increase the viscosity at higher shear rates, decrease the fluid loss, or provide other characteristics to the fluids.

The minimum concentration of the polysaccharide polymer required to increase the low shear rate viscosity of the oil-in-water emulsion can be determined by routine testing. Thus the minimum concentration will be an amount sufficient to impart to the emulsion the desired low shear rate viscosity. Generally the emulsions will contain a concentration from about 0.7 kg/m³ (0.25 ppb) to about 17.1 kg/m³ (6 ppb), preferably from about 1.4 kg/m³ (0.5 ppb) to about 14.25 kg/m³ (5 ppb).

The oil-in-water base borehole fluids of this invention generally will contain materials well known in the art to provide various characteristics or properties to the fluid. Thus the fluids may contain one or more viscosifiers or suspending agents in addition to the polysaccharide required, weighting agents, corrosion inhibitors, soluble salts, biocides, fungicides, seepage loss control additives, bridging agents, deflocculants, shale control additives, pH control additives, additional emulsifiers, and other additives as desired.

The oil-in-water borehole fluids may contain one or more materials which function as encapsulating or fluid loss control additives to restrict the entry of liquid from the fluid to the contacted shale. Representative materials known in the art include partially solublized starch, gelatinized starch, starch derivatives, cellulose derivatives, humic acid derivatives, lignin derivatives, lignosulfonates, gums, synthetic water soluble polymers, and mixtures thereof.

The emulsions of this invention preferably have a pH in the range from about 7.5 to about 11.5, most preferably from 8 to about 11. The pH can be obtained as is well known in the art by the addition of bases to the fluid, such as potassium hydroxide, potassium carbonate, potassium humate, sodium hydroxide, sodium carbonate, sodium humate, magnesium oxide, calcium oxide, calcium hydroxide, zinc oxide, and mixtures thereof.

If desired, water soluble potassium compounds can be incorporated into the fluids of this invention to increase the potassium ion content thereof. Thus it is known to add potassium chloride, potassium formate, potassium acetate, and the like to fluids to enhance the shale stabilizing characteristics of the fluids.

Polysaccharide-containing fluids can be prepared by hydrating the polysaccharide in the aqueous liquid, adding the OSM thereto, and thereafter adding the oleaginous liquid and other materials as desired.

As indicated herein, the combination of the OSM and the oleaginous liquid increases the viscosity of the oil-in-water emulsions. The additional addition of the AEMOOH, preferably lime, to the fluid further increases the viscosity of the fluid.

There has been disclosed in co-pending patent application serial no. 09/121,713 filed Jul. 24, 1998, incorporated herein by reference, aphron-containing well drilling and servicing fluids containing a polymer which imparts a LSRV of at least 10,000 centipoise and a shear thinning index of at least 10 to the fluid, the OSM as disclosed herein, a foaming surfactant and aphrons.

The oil-in-water emulsion of the present invention may also contain aphrons. This is accomplished by incorporating a compatible foaming surfactant into the emulsion and thereafter generating the aphrons. The aphrons can be generated by means known in the art. The book by Felix Sebba entitled "Foams and Biliquid Foams-Aphrons", John Wiley & Sons, 1987, incorporated herein by reference, is an excellent source on the preparation and properties of aphrons, i.e., microbubbles. Other methods of generating aphrons are disclosed in Michelsen et al. U.S. Pat. No. 5,314,644, incorporated herein by reference, and Yoon et al. U.S. Pat. No. 5,397,001, incorporated herein by reference.

The surfactant for generating the aphrons should be compatible with the oil-in-water emulsion such that the LSRV or the stability of the emulsion are not appreciably decreased. The surfactant may be non-ionic, anionic, cationic, or amphoteric as determined by routine testing.

In order to more completely describe the invention, the following non-limiting examples are given. In these examples and in this specification, the following abbreviations may be used: cc=cubic centimeters; v=volume; kg=kilogram; m³ =cubic meter; ppb=pounds per 42 gallon barrel; ppg=pounds per gallon; API=American Petroleum Institute; PV=API plastic viscosity in centipoise; YP=API yield point in pounds per 100 square feet; rpm=revolutions per minute; OS=off-scale; LSRV=low shear rate viscosity in centipoise as determined with a Brookfield Viscometer at 0.5 rpm; STI=the shear thinning index obtained with a Brookfield Viscometer, which is the ratio of the 0.5 rpm viscosity to the 100 rpm viscosity; AEMOOH=alkaline earth metal oxide or hydroxide; OSM=oligosaccharide mixture as set forth hereinbefore.

The Fann rheology and fluid loss were determined by the procedures set forth in the American Petroleum Institute's Recommended Practice 13B-1.

EXAMPLE 1

An oil-in-water emulsion was prepared containing 3.35 ppb of OSM, 2.0 ppb of lime, and 50% by volume diesel oil. The Fann API rheology was obtained initially and after aging at 185° F. for 16 hours. The data obtained are as follows: Initial--600 rpm=130, 300 rpm=85, 200 rpm=64, 100 rpm=39, 6 rpm=6, 3 rpm=4.5, PV (cp)=45, and YP (lb/100 sq.ft.)=40. Static Aged at 185° F. for 16 hours and mixing--600 rpm=118, 300 rpm=80, 200 rpm=55, 100 rpm=30, 6 rpm=2.5, 3 rpm=2, PV (cp)=38, YP (lb/100 sq.ft.)=42. The OSM is the water soluble fraction resulting from the thermal hydrolysis of lignocellulose materials, in particular, pine wood. The data indicate the excellent stability of the emulsions of this invention.

EXAMPLE 2

Oil-in-water emulsions were prepared containing the concentrationis of OSM, lime, water, and an internal olefin base oil set forth in Table A. The emulsions were evaluated for their Fann API rheology and Brookfield viscosities. The data obtained are set forth in Table A.

                                      TABLE A                                      __________________________________________________________________________     Emulsion                                                                              1  2    3    4    5    6   7    8   9*                                  __________________________________________________________________________     H.sub.2 O, bbl                                                                        0.3                                                                               0.3  0.3  0.5  0.5  0.7 0.7  0.7 0.38                                OSM, ppb                                                                              2.0                                                                               2.0  2.0  3.5  3.5  8.0 20.0 40.0                                                                               181                                 Lime, ppb                                                                             0  1.0  2.0  2.0  5.0  2.0 5.0  5.0 0                                   Olefin, bbl                                                                           0.7                                                                               0.7  0.7  0.5  0.5  0.3 0.3  0.3 0.3                                 Fann Rheology                                                                  600 rpm                                                                               73 113  OS   67   66   26  39   31  OS                                  300 rpm                                                                               43 91   --   39   41   14  25   18  --                                  3 rpm  1  30   --   2    3    0.5 0.5  0.5 --                                  PV, cp 30 22   --   28   25   12  14   13  --                                  YP, lb/100 ft.sup.2                                                                   13 69   --   11   16   2   11   5   --                                  Brookfield Viscosities                                                         0.5 rpm                                                                               600                                                                               80,000                                                                              320,000                                                                             16,200                                                                              16,400                                                                              9,400                                                                              22,800                                                                              2,800                                                                              2,500                               100 rpm                                                                               99 800  400  171  178  82  193  74  947                                 STI    6  100  800  95   92   115 118  38  3                                   __________________________________________________________________________      *Added 318.5 g of a slurry comprising 181 g of OSM and 137.5 g of water =      0.7 bbl aqueous phase.                                                    

What is claimed is:
 1. An oil-in-water emulsion comprising ( 1) an aqueous continuous phase, (2) an oligosaccharide mixture composed of sugar units selected from the group consisting of arabinose, mannose, galactose, glucose, xylose, and mixtures thereof, and which consists primarily of pentosans, hexosans, and mixtures thereof, containing from one to about ten combined sugar units, and (3) an oleaginous liquid emulsified into the aqueous phase.
 2. The oil-in-water emulsion of claim 1 which additionally contains an alkaline earth metal oxide or hydroxide.
 3. The oil-in-water emulsion of claim 1 which additionally contains lime.
 4. The oil-in-water emulsion of claim 1 which additionally contains a foaming surfactant and aphrons generated therein.
 5. The oil-in-water emulsion of claim 4 which additionally contains an alkaline earth metal oxide or hydroxide.
 6. The oil-in-water emulsion of claim 4 which additionally contains lime.
 7. The oil-in-water emulsion of claim 1, 2, 3, 4, 5, or 6, wherein the oligosaccharide mixture comprises the water soluble portion of thermally hydrolyzed lignocellulose.
 8. The oil-in-water emulsion of claim 1, 2, 3, 4, 5, or 6, wherein the emulsion contains from about 0.5 ppb to about 150 ppb of the oligosaccharide mixture.
 9. The oil-in-water emulsion of claim 2 or 5 wherein the emulsion contains from about 0.5 ppb to about 150 ppb of the oligosaccharide mixture and from about 0.5 ppb to about 3 ppb of the alkaline earth metal oxide or hydroxide.
 10. The oil-in-water emulsion of claim 7 wherein the emulsion contains from about 5% to about 75% by volume of the oleaginous liquid. 